EP0849337B1 - Particules d'oxyde de métal fluorées en surface, procédé pour les préparer et leur utilisation - Google Patents

Particules d'oxyde de métal fluorées en surface, procédé pour les préparer et leur utilisation Download PDF

Info

Publication number
EP0849337B1
EP0849337B1 EP97122415A EP97122415A EP0849337B1 EP 0849337 B1 EP0849337 B1 EP 0849337B1 EP 97122415 A EP97122415 A EP 97122415A EP 97122415 A EP97122415 A EP 97122415A EP 0849337 B1 EP0849337 B1 EP 0849337B1
Authority
EP
European Patent Office
Prior art keywords
fluorinated
particulates
metal oxide
titanium dioxide
particulate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97122415A
Other languages
German (de)
English (en)
Other versions
EP0849337A2 (fr
EP0849337A3 (fr
Inventor
Ryuji c/o Showa Denko K.K. Monden
Chozo c/o Showa Denko K.K. Inoue
Jun c/o Showa Titanium Co. Ltd. Tanaka
Hiroyuki c/o Showa Denko K.K. Hagihara
Hiroyasu c/o Showa Denko K.K. Taguchi
Hiroyuki c/o Showa Denko K.K. Takahashi
Manabu c/o Showa Denko K.K. Ohira
Katsura c/o Showa Denko K.K. Ito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of EP0849337A2 publication Critical patent/EP0849337A2/fr
Publication of EP0849337A3 publication Critical patent/EP0849337A3/fr
Application granted granted Critical
Publication of EP0849337B1 publication Critical patent/EP0849337B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/145—After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4584—Coating or impregnating of particulate or fibrous ceramic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5018—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with fluorine compounds
    • C04B41/5019—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with fluorine compounds applied from the gas phase, e.g. ocratation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/54—Pigments; Dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium

Definitions

  • the present invention relates to the manufacture of surface-fluorinated metal oxide particulates. More specifically, the present invention relates to surface-fluorinated metal oxide particulates whose surface affinity being controlled from 'hydrophilic' to 'hydrophobic' and which has improved stability, water repellence and dispersibility, a process for manufacturing the same and use of the same.
  • Metal oxide particulates are used for a wide variety of applications and useful as raw materials of paints, matting agents for synthetic fibers, printing ink, cosmetics, opal glass, etc. and as coloring agents for rubbers and resins, pigments; and the like.
  • the surface of a metal oxide particulate is usually covered with hydroxyl groups and exhibits hydrophilicity. Accordingly, when the metal oxide particulates are blended in a resin, a paint or a cosmetic, a large number of surface treatments such as treatment with a higher fatty acid, treatment with an organic silicon compound, silica-alumina treatment and treatment with various coupling agents, are being attempted and practiced so as to improve dispersibility, for example, of titanium oxide. Also, there has been attempted surface treatment of aluminum oxide or silicon oxide with a silylating agent or the like.
  • JP-A-59-184263 discloses a method of adding sodium fluoride to a suspension slurry of titanium oxide and stirring the mixture.
  • JP-A in the case when titanium oxide is an ultrafine particulate, coagulation in the drying process is intensified and good dispersibility cannot be obtained even if the matters coagulated are crushed.
  • the fluorine atom is not bonded directly to the titanium atom and it cannot be said that the titanium oxide surface is fluorinated or modified with fluorine.
  • JP-A-61-215216 discloses a method of using an organic fluorine compound as a hydrophobicity-imparting substance in the production of hydrophobic spherical titanium oxide particulates. However, also in this case, the titanium oxide surface is substantially not modified with fluorine.
  • JP-A-3-40919 discloses a method of bringing freon gas into contact with titanium oxide ultrafine particulates and modifying their surface with fluorine at a high temperature of from 200 to 400 °C.
  • a high temperature of from 200 to 400 °C.
  • use of the reaction temperature as high as 200 °C or more results in a thermal efficiency which is not always good.
  • the present invention is to solve these problems involved in the conventional techniques and provides surface fluorinated metal oxide particulates and a process for manufacturing the same.
  • Another object of the present invention is to provide a thermoplastic resin composition containing surface-fluorinated titanium oxide particulate pigment as a specific use of surface-fluorinated titanium oxide particulates.
  • the present inventors have found that when a metal oxide particulate is reacted with fluorine, there can be obtained a substantially surface-fluorinated metal oxide particulate, which is accordingly water-repellent and oil-repellent.
  • a surface-fluorinated titanium oxide particulate has been improved on light stability, water-repellence, and dispersibility over the conventional titanium oxide particulates and accordingly is particularly suitable for use in thermoplastic resin compositions for photographic resin coating paper such as highly white thin film composed of a thermoplastic resin containing a titanium oxide particulate as a white pigment.
  • the present invention provides surface-fluorinated metal oxide particulates, a process for manufacturing the same and a thermoplastic resin composition containing surface-fluorinated titanium oxide particulate pigment as below.
  • Fig. 1 is a schematic drawing showing a reactor used in tests for confirming the catalyst activity on a photochemical reaction of surface-fluorinated titanium oxide particulates of the present invention.
  • the process for manufacturing metal oxide particulates whose surface is fluorinated or modified with fluorine is characterized by reacting metal oxide particulates with fluorine to substantially fluorinate the surface of the particulates or by controlling the fluorination in any desired ratio.
  • substantially means that nearly the entire surface of a metal oxide particulate is modified with fluorine, i.e., fluorinated. However, the surface does not have to be modified in 100% with fluorine or uniformly over all the surface.
  • the ratio of fluorination of the surface of particulates is determined from all the elements existing from the surface of the particulates to the depth of about 100 ⁇ as measured by XPS (X-ray photoelectron spectroscopy).
  • metal oxide as used in the present invention means an oxide of a metal, and examples thereof include oxides of aluminum, silicon, silver, copper, zirconium, zinc, tin, germanium and tantalum. in particular, oxides of aluminum and silicon are preferred.
  • the particle diameter, specific surface area, crystal type and the like of the metal oxide particulate used as the raw material are not limited particularly and various metal oxide particulates may be used. Usually, those having an average primary particle size of 1,000 ⁇ m or less, preferably 100 ⁇ m or less, more preferably from 0.005 to 1 ⁇ m, and a very large specific surface area of 0.01 m 2 /g or more, preferably from 3 to 300 m 2 /g (according to the BET method) are used.
  • the aluminum oxide may be any. of noncrystalline, ⁇ -alumina and ⁇ -alumina; and the silicon oxide may be either of silicic acid anhydride and synthetic silicic acid.
  • the fluorination reaction for manufacturing metal oxide particulates used as the raw material is a gas phase process, which is carried out, for example, as follows.
  • the above-described metal oxide particulates are filled into a reactor of atmospheric gas phase flow system or the like, the reactor is heated at a predetermined temperature, fluorine gas is filled into the reactor, and these are reacted for a predetermined time to effect surface fluorination treatment.
  • the heating temperature of the reactor in other words, the reaction temperature is usually from 0 to 200 °C, preferably from 20 to 150 °C.
  • the reaction time is usually from instant to 3 hours, preferably from instant to 1 hour.
  • the flow rate of fluorine gas is usually from 0.1 to 100 ml/g ⁇ min, preferably from 0. 5 to 50 ml/g ⁇ min. In the case of small amount flowing, a batch system can be used.
  • the fluorine gas concentration is suitably 100%. However, at least 0.01% by volume, preferably at least 0.1% by volume, and more preferably at least 1% by volume of fluorine gas diluted with nitrogen or argon is also usable.
  • concentration of fluorine gas and/or reaction time allows easy control of fluorination ratio on the surface of a particulate.
  • the surface-fluorinated metal oxide particulates obtained by the method of the present invention described above have an average primary particle diameter of 1,000 ⁇ m or less, preferably 100 ⁇ m or less, more preferably from 0.005 to 1 ⁇ m (fine particulate or ultrafine particulate).
  • the surface-fluorinated metal oxide particulate of the present invention has a very large specific surface area of 0.01 m 2 /g or more, preferably from 3 to 300 m 2 /g (according to the BET method).
  • the surface-fluorinated metal oxide particulates of the present invention exhibit water-repellent and oil-repellent effects and are excellent in resistance to acids and alkalis. Further, the surface-fluorinated metal oxide particulates of the present invention have excellent dispersibility, which is convenient when they are added and blended with Teflon resin for the purpose of improving light stability, weatherability, hiding power, and whiteness, controlling refractive index, absorbing ultraviolet rays, and so on.
  • the surface-fluorinated metal oxide particulates of the present invention is very useful as an additive to weatherable paints, weatherable resins, cosmetics and so on.
  • the surface of metal oxide particulates can be freely fluorinated in any desired ratio very easily and efficiently so that the present invention is very useful in industries.
  • thermoplastic Resin Composition Containing Surface-Fluorinated Titanium Oxide Pigment Containing Surface-Fluorinated Titanium Oxide Pigment
  • Titanium dioxide is widely used as a white pigment or the like for use in photographic thermoplastic resin composition for photographic resin-coated paper such as highly white thin film and the like. Titanium dioxide blended for such a purpose is surface treated with aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide or hydrates thereof in order to inhibit optical activity or improve weatherability or dispersibility as a pigment. Of these, a surface treatment with aluminum oxide hydrate for inhibiting optical activity is generally used and various processes have been proposed therefor.
  • U.S. Patent 4,416,699 proposes a process including the steps of (1) adding a predetermined amount of titanium dioxide to water to form a slurry; (2)adjusting the temperature of the slurry to a predetermined range; (3) adding a soluble aluminum compound to the slurry and allowing it to dissolve; and (4) aging the mixture at a predetermined temperature and at a predetermined pH for a predetermined period of time.
  • JP-A-55-154317 proposes a process which includes the steps of dispersing 100 to 500 g/l, preferably 250 to 400 g/l, of titanic acid or titanium dioxide in water to form a slurry; adding sodium aluminate and optionally a dispersant, if desired, to the slurry in order to well disperse titanic acid or titanium dioxide; and neutralizing the slurry with an acid to deposit aluminum oxide hydrate.
  • the amount of the inorganic oxide or hydrates thereof used in the treatment is generally 0.1 to 5 parts by weight per 100 parts by weight of titanium dioxide.
  • thermoplastic resin composition containing titanium dioxide pigment In order to coat one or both surfaces of a substrate such as paper or polyester with thermoplastic resin composition containing titanium dioxide pigment, there is generally used a melt-extrusion lamination processing method.
  • the resin-coated paper is required to have even more excellent whiteness and high opacity.
  • the coating film is in a poor condition due to poor dispersion of titanium dioxide.
  • the term "poor condition of a coating film” means that the film has a poor surface smoothness, bubbles are contained in the film or otherwise undesirable condition, which causes a further problem that lamination molding has to be interrupted or stable, high speed molding is difficult to carry out.
  • the present inventors have investigated extensively on a resin composition and its master batch with view to (1) realizing a good surface condition such that when a resin containing titanium dioxide to be added as a filler mainly for imparting high opacity or whiteness is coated in the form of a thin film on a carrier such as paper or the like, use of an increased concentration of the filler gives rise to a minimized amount of "microgrits," which are relatively solid and fine foreign matter like prongs, and "gel,” i.e., relatively soft, fine hill-like foreign matter occurring on the film surface; (2) preventing the occurrence of troubles upon processing when melt extrusion coating is carried out in order to obtain such a resin coated paper or resin coated carrier; and (3) preventing melt-flow-rate (MFR) from decreasing due to addition of titanium dioxide pigment and increasing its fluidity.
  • MFR melt-flow-rate
  • the present inventors have confirmed the followings.
  • a titanium dioxide pigment that has an excellent dispersibility in a thermoplastic resin, suffers from less decrease in MFR and has an improved fluidity.
  • surface-fluorinated titanium oxide particulates are most suitable.
  • the main cause of poor dispersibility upon blending titanium dioxide in a resin is largely attributable to the moisture content in the resin composition and master batch. Accordingly, it is important to control the moisture content of the resin composition and master batch to a certain low level (10 to 1,400 ppm).
  • the thermoplastic resin composition containing surface-fluorinated titanium oxide particulate pigment and its master batch of the present invention are reached based on the knowledge.
  • Titanium dioxide which is the raw material of the surface-fluorinated titanium oxide particulates used in the thermoplastic resin composition of the present invention may be any one of noncrystalline, 'anatase, brookite, and rutile. Those manufactured by any one of a chlorine process, a sulfuric acid process, a gas phase process, a liquid phase process and the like.
  • the surface fluorination of titanium oxide can be carried out by the above-mentioned process.
  • the fluorine content of the surface-fluorinated titanium oxide particulates used in the present invention as determined by XPS is preferably 0.001 to 61% by weight, more preferably 0.1 to 61% by weight.
  • the particle diameter of titanium dioxide is desirably an average particle diameter of 0.02 to 1.0 ⁇ m in order to improve optical properties of the thermoplastic resin composition. Outside this range, optical properties such as light scattering, color hue and the like are aggravated considerably.
  • the titanium dioxide described above is excellent in improvement of light stability, water repellence and dispersibility.
  • an other metal oxide-containing titanium dioxide which contains one or more of aluminum oxide, silicon oxide, zirconium oxide and the like, in an amount of 0.001 to 0.2 part by weight per 100 parts by weight of titanium dioxide may be fluorinated in order to increase the dispersibility of titanium dioxide at the time of preparing a master batch.
  • the fluorine content of the surface-fluorinated titanium oxide particulates used in the present invention as determined by XPS is preferably 0.001 to 61% by weight, more preferably 0.1 to 61% by weight, of the titanium dioxide surface containing the other metal oxide.
  • Kneader is not limited particularly but there can be used various types of kneaders including a batch type one such as Banbury mixer, a twin-screw kneader, a single-screw extruder having a kneading function and so on.
  • thermoplastic resin used in the resin composition of the present invention examples include polyolefins such as polyethylene, polypropylene, ethylene/propylene copolymers (inclusive of random or block copolymers), polystyrenes, etc., ABS resin, AS resin, polyvinyl chlorides, polyesters, polyacetals, polycarbonates, poly(aromatic cyclic ether)s, poly (aromatic cyclic ester)s, polyamides, polysulfones, and the like. Preferred are polyolefins.
  • thermoplastic resin as described above and surface-fluorinated titanium oxide particulates may be kneaded to form the surface-fluorinated titanium dioxide pigment-containing thermoplastic resin composition or a master batch may be prepared which contains the surface-fluorinated titanium oxide particulate pigment in a high content.
  • a metal soap such as zinc stearate, an antioxidant or the like may be added prior to kneading the surface-fluorinated titanium oxide particulates with the thermoplastic resin or upon kneading in order to increase the lubricity or dispersibility of the composition.
  • the metal soap is added desirably in an amount of 0.1 to 10 parts by weight per 100 parts by weight of titanium dioxide. It is desired that the antioxidant be added in an amount of 0.001 to 0.1 part by weight per 100 parts by weight of titanium dioxide.
  • a high concentration of titanium dioxide pigment which is subjected to the surface-fluorination treatment as described above, is kneaded with a resin, and a master batch processed into pellets is prepared at first, followed by blending an uncolored resin (containing no pigment) and the master batch to form a resin composition.
  • the master batch contains 30 to 80% by weight of the surface-fluorinated titanium dioxide pigment per 100 parts by weight of the raw material resin.
  • the resin composition contains 20 to 80% by weight of the surface-treated titanium dioxide pigment per 100 parts by weight of the raw material resin.
  • the concentration of the pigment when the concentration of the pigment is below 30% by weight, the concentration of the pigment is too low to obtain sufficient optical properties such as high opacity and whiteness when a resin composition is formed therefrom, while the pigment concentration of above 80% by weight is undesirable since it is difficult to uniformly disperse the pigment during the preparation of a master batch.
  • the pigment concentrations of below 20% by weight result in a difficulty of obtaining high optical properties, while use of a pigment concentration of above 80% by weight is undesirable since film defect such as foaming tends to occur due to vaporization of the moisture that is incorporated as entrained by the pigment upon the formation of a high whiteness thin film.
  • thermoplastic resin composition of the present invention having a water content adjusted to a low level that is not attained heretofore and a master batch thereof cannot be obtained until the above-described manufacturing process is used.
  • the raw material resin itself manufactured by an ordinary process has a sufficiently low water content of about 500 ppm or less, film defects occur due to contamination of water during addition and blending of hygroscopic metal oxide particulates.
  • the water content is decreased to a low level during the reaction with fluorine of the surface of titanium oxide or titanium oxide containing aluminum oxide, silicon oxide, zirconium oxide or the like and this low level of water absorption is maintained so that the incorporation of water into the resin composition is prevented during the mixing of the resin with the surface-fluorinated titanium oxide particulates, thus providing a resin composition containing the surface-fluorinated metal oxide particulates with its water content being controlled to a low level.
  • surface-fluorinated titanium oxide particulates or surface-fluorinated titanium oxide containing one or more other metal oxides obtained by a gas phase process can facilitate the manufacture of the resin composition of the present invention having a water content of 10 to 1,400 ppm as determined as described below and a master batch thereof.
  • water content refers to a value obtained by the amount (g) of moisture as determined by moisture conditioning 3 g of the composition in an atmosphere of 60 °C and relative humidity of 60% for 4 hours, exposing the thus conditioned composition to an air stream of absolute humidity of 0.009 kg H 2 O/kg of dry air at 80 °C for 4 hours, degassing the composition at 300 °C for 30 minutes, measuring the moisture content (g) of the composition using a Karl-fischer moisture meter, and dividing the amount of the moisture thus obtained by the surface-fluorinated titanium dioxide content (g).
  • the water content is controlled to a sufficiently low level as described above and the surface-fluorinated titanium oxide particulates are used as the titanium dioxide, which is well dispersed in the thermoplastic resin and which has improved fluidity so that a decrease in MFR hardly occurs and accordingly, when the resin composition is molded into a thin film with an increased content of the surface-fluorinated titanium oxide particulate, there can be obtained resin-coated paper or the like with a good film condition which is excellent in surface smoothness and fluidity.
  • the surface-fluorinated metal oxide particulates and process for manufacturing the same of the present invention are described in greater detail below by referring to the Examples. However, the present invention should not be construed as being limited to these Examples. In the following, particularly, titanium oxide, aluminum oxide and silicon oxide are described.
  • the specific surface area of metal oxide particulates is measured by the BET method.
  • the fluorine contents of the surface of the particulates indicate the ratio (% by weight) to the total constituent elements on the surface of specimen measured by XPS but excludes the carbon introduced by contamination.
  • Titanium dioxide particulate (reference only):
  • Titanium tetrachloride as a raw material was introduced at a rate of 189 g/hr into a vaporizer heated at 140 °C together with 1.05 Nm 2 /hr of nitrogen gas as a carrier gas, and the raw material was completely vaporized.
  • 1,200 g/hr of water was introduced into a vaporizer heated at 450 °C together with 2.26 Nm 2 /hr of nitrogen gas to prepare superheated steam.
  • This superheated steam was introduced into a reactor having an inner diameter of 30 mm simultaneously with the vaporized raw material and hydrolysis reaction was performed at 260 °C.
  • titanium dioxide particulates were obtained.
  • the particulates were observed through an electron microscope and found to have an average primary particle size of 0.02 ⁇ m. Further, the particulates were verified to be noncrystalline by the X-ray diffraction pattern. Furthermore, the specific surface area determined by the BET method using nitrogen gas was 55 m 2 /g.
  • Aluminum chloride as a raw material was introduced at a rate of 315 g/hr into a vaporizer heated at 300 °C together with 1.05 Nm 2 /hr of nitrogen gas as a carrier gas, and the raw material was completely vaporized.
  • 1,200 g/hr of water was introduced into a vaporizer heated at 450 °C together with 2.26 Nm 2 /hr of nitrogen gas to prepare superheated steam.
  • This superheated steam was introduced into a reactor having an inner diameter of 30 mm simultaneously with the vaporized raw material and hydrolysis reaction was performed at 260 °C.
  • aluminum oxide particulates were obtained. The particulates were observed through an electron microscope and found to have an average primary particle size of 0.02 ⁇ m. Further, the particulates were verified to be noncrystalline by the X-ray diffraction pattern. Furthermore, the specific surface area determined by the BET method using nitrogen gas was 100 m 2 /g.
  • Silicon tetrachloride as a raw material was introduced at a rate of 401 g/hr into a vaporizer heated at 100 °C together with 1.05 Nm 2 /hr of nitrogen gas as a carrier gas, and the raw material was completely vaporized.
  • 1,200 g/hr of water was introduced into a vaporizer heated at 450 °C together with 2.26 Nm 2 /hr of nitrogen gas to prepare superheated steam.
  • This superheated steam was introduced into a reactor having an inner diameter of 30 mm'simultaneously with the vaporized raw material and hydrolysis reaction was performed at 260 °C.
  • silicon dioxide particulates were obtained.
  • the particulates were observed through an electron microscope and found to have an average primary particle size of 0.02 ⁇ m. Further, the particulates were verified to be noncrystalline by the X-ray diffraction pattern. Furthermore, the specific surface area determined by the BET method using nitrogen gas was 120 m 2 /g.
  • titanium dioxide particulates (specific surface area: 55 m 2 /g) prepared in Manufacturing Example 1 were filled into a reactor of atmospheric gas phase flow system and calcined as the pretreatment at 200 °C for 1 hour under reduced pressure. After cooling to 20 °C, gas obtained by diluting fluorine gas with nitrogen gas (fluorine gas content: 20% by volume) was charged into this reactor for 15 minutes to perform surface fluorination. The resulting surface-fluorinated titanium dioxide particulate had a specific surface area of 55 m 2 /g and thus, maintained its high specific surface area. The fluorine content on the surface of titanium dioxide particulate was quantified by XPS and as a result, the fluorine atom was 10%. The results obtained are shown in Table 1.
  • titanium dioxide particulates (specific surface area: 55 m 2 /g) prepared in Manufacturing Example 1 were filled into a reactor of atmospheric gas phase flow system and calcined as the pretreatment at 200 °C for 1 hour under reduced pressure. After cooling to 70 °C, gas obtained by diluting fluorine gas with nitrogen gas (fluorine gas content: 20% by volume) was charged into this reactor for 15 minutes to perform surface fluorination. The resulting surface-fluorinated titanium dioxide particulate had a specific surface area of 51 m 2 /g and thus, maintained its high specific, surface area. The fluorine content on the surface of titanium dioxide particulate was quantified by XPS and as a result, the fluorine atom was 14%. The results obtained are shown in Table 1.
  • titanium dioxide particulates (specific surface area: 55 m 2 /g) prepared in Manufacturing Example 1 were filled into a reactor of atmospheric gas phase flow system and gas obtained by diluting fluorine gas with nitrogen gas (fluorine gas content: 1% by volume) was charged into this reactor at room temperature for 15 minutes to perform surface fluorination.
  • the resulting surface-fluorinated titanium dioxide particulate had a specific surface area of 55 m 2 /g and thus, maintained its high specific surface area.
  • the fluorine content on the surface of titanium dioxide particulate was quantified by XPS and as a result, the fluorine atom was 12%.
  • the photoactivity was sufficiently restrained. The results obtained are shown in Table 1.
  • titanium dioxide particulates (specific surface area: 55 m 2 /g) prepared in Manufacturing Example 1 were filled into a reactor of atmospheric gas phase flow system and gas obtained by diluting fluorine gas with nitrogen gas (fluorine gas content: 20% by volume) was charged into this reactor at room temperature for 15 minutes to perform surface fluorination.
  • the resulting surface-fluorinated titanium dioxide particulate had a specific surface area of 53 m 2 /g and thus, maintained its high specific surface area.
  • the fluorine content on the surface of titanium dioxide particulate was quantified by XPS and as a result, the fluorine atom was 22%. The results obtained are shown in Table 1.
  • titanium dioxide particulates (specific surface area: 55 m 2 /g) prepared in Manufacturing Example 1 were filled into a reactor of atmospheric gas phase flow system and gas obtained by diluting fluorine gas with nitrogen gas (fluorine gas content: 20% by volume) was charged into this reactor at 70 °C for 15 minutes to perform surface fluorination.
  • the resulting surface-fluorinated titanium dioxide particulate had a specific surface area of 52 m 2 /g and thus, maintained its high specific surface area.
  • the fluorine content on the surface of titanium dioxide particulate was quantified by XPS and as a result, the fluorine atom was 24%. The results obtained are shown in Table 1.
  • the resulting titanium dioxide particulate treated with fluoride had a specific surface area of 35 m 2 /g reduced from that before the treatment of 55 m 2 /g.
  • the surface fluorine content was 7 atm %.
  • Table 1 Fluorine Gas Concentration Temperature at Modification with Fluorine Surface Fluorine Content Specific Surface Area
  • Example 8 20 % 70 °C 31 % 95 m 2 /g
  • an oxygen absorption rate was measured using an apparatus shown in Fig. 1 by referring to the study of Kato et al ( Kogyo Kagaku Zasshi (Journal of Industrial Chemistry) , 63, 5, 748-750 (1960)) and the value obtained was shown as the photochemical activity.
  • the measurement was performed by irradiating ultraviolet rays (1) while stirring with a stirrer (3) under conditions such that the amount of tetralin charged in a Pyrex glass reactor (5) was 20 ml, the amount of titanium dioxide charged was 0.02 g, the atmosphere was O 2 and the reaction temperature was 40.1 °C in an incubator (2).
  • the pressures were recorded using a differential pressure gauge (4) and changes in pressure were plotted every time period and the gradient (pressure change: mmH 2 O/minute) was taken as the oxygen absorption rate.
  • Table 2 shows that fluorination of the surface of titanium dioxide particulates with fluorine gas allows inhibition of photochemical catalyst activity of titanium dioxide (Examples 1 to 3) and adjustment of the concentration of fluorine gas used upon fluorination reaction enables one to control the photochemical catalyst activity (Examples 13 and 14). Further, NaF-treated titanium dioxide particulates having an apparent surface fluorine atom of 7% (Comparative Example 1) had a photochemical catalyst activity which is not inhibited as compared with that prior to the treatment, which suggests that the surface of the NaF-treated titanium dioxide particulates were not substantially fluorinated.
  • thermoplastic resin composition Manufacture of surface-fluorinated titanium dioxide particulates for blending into thermoplastic resin composition
  • titanium dioxide particulates (specific surface area: 8 m 2 /g, particle diameter: 0.21 ⁇ m) were filled into a reactor of atmospheric gas phase flow system and calcined as the pretreatment at 200 °C for 1 hour under reduced pressure. After cooling to 20 °C, gas obtained by diluting fluorine gas with nitrogen gas (fluorine gas content: 5% by volume) was charged into this reactor for 15 minutes to perform surface fluorination. The resulting surface-fluorinated titanium dioxide particulate had a specific surface area of 8 m 2 /g and thus, maintained its high specific surface area. The fluorine content on the surface of titanium dioxide particulate was quantified by XPS and as a result, the fluorine atom was 10%.
  • the moisture content of the master batch was measured by the above-described method was 220 ppm.
  • the master batch was kneaded with the above-described low density polyethylene (JRex LDL 133K) containing no pigment in a proportion of 1 : 0.667 using a Lab Plastomil (a 20 ⁇ extruder; Toyo Seiki Co., Ltd.) at 150 °C for 30 minutes to prepare a resin composition.
  • the composition had a moisture content of 150 ppm.
  • a thin film layer of 20 ⁇ m thick was formed on a surface of 200 ⁇ m-thick high quality paper by a high temperature melt lamination method.
  • the master batch was kneaded with the above-described polyimide containing no pigment in a proportion of 1 : 0. 67 using a Lab Plastomil (a 20 ⁇ extruder; Toyo Seiki Co., Ltd.) at 250 °C for 30 minutes to prepare a resin composition.
  • the resin composition had a moisture content of 110 ppm.
  • the moisture content of the master batch was measured by the above-described method was 1940 ppm.
  • the master batch was kneaded with the above-described low density polyethylene containing no pigment in a proportion of 1 : 0. 67 using a Lab Plastomil (a 20 ⁇ extruder; Toyo Seiki Co., Ltd.) at 150 °C for 30 minutes to prepare a resin composition.
  • the composition had a moisture content of 1990 ppm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Cosmetics (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Claims (17)

  1. Procédé de production de particules d'oxyde métallique fluoré en surface comprenant le chauffage de particules d'oxyde métallique puis la réaction des particules d'oxyde métallique avec du gaz fluor, où l'oxyde métallique est choisi dans le groupe consistant en les oxydes d'aluminium, de silicium, d'argent, de cuivre, de zirconium, de zinc, de germanium et de tantale.
  2. Procédé de production de particules d'oxyde métallique fluoré en surface selon la revendication 1 où on utilise un gaz contenant du fluor qui contient du fluor et un gaz diluant.
  3. Procédé de production de particules d'oxyde métallique fluoré en surface selon la revendication 2 où le gaz diluant est l'azote ou l'argon.
  4. Procédé de production de particules d'oxyde métallique fluoré en surface selon l'une quelconque des revendications 1 à 3 où la durée de la réaction et/ou la concentration de gaz du réactif fluoré sont régulées pour obtenir une particule d'oxyde métallique fluoré en surface ayant un taux de fluoration de surface régulé.
  5. Procédé de production de particules d'oxyde métallique fluoré en surface selon l'une quelconque des revendications 1 à 4 où l'oxyde métallique est choisi parmi l'oxyde d'aluminium et l'oxyde de silicium.
  6. Particule d'oxyde métallique fluoré en surface pouvant être obtenue par le procédé selon l'une quelconque des revendications 1 à 5.
  7. Particule d'oxyde métallique selon la revendication 6 qui a une surface sensiblement fluorée.
  8. Composition de résine thermoplastique comprenant une résine thermoplastique et une particule d'oxyde métallique fluoré en surface où ladite particule d'oxyde métallique est telle que revendiquée dans la revendication 6 ou 7.
  9. Composition de résine thermoplastique contenant un pigment de particules d'oxyde de titane fluoré en surface qui est une composition de résine thermoplastique contenant un pigment de dioxyde de titane pour former un revêtement sur un substrat, où la composition comprend le pigment de particules d'oxyde de titane fluoré en surface pouvant être obtenu par une réaction comprenant le chauffage de particules d'oxyde de titane puis la réaction des particules d'oxyde de titane avec du gaz fluor, où le pigment de particules d'oxyde de titane fluoré en surface a une surface sensiblement fluorée et une teneur en eau de 10 à 1 400 ppm, déterminée par conditionnement à l'humidité de 3 g de la composition dans une atmosphère de 60°C et d'une humidité relative de 60 % pendant 4 heures, exposition de la composition ainsi conditionnée à un courant d'air d'humidité absolue de 0,009 kg H2O/kg d'air sec à 80°C pendant 4 heures, dégazage de la composition à 300°C pendant 30 minutes, mesure de la teneur en humidité (g) de la composition au moyen d'un appareil de mesure de l'humidité de Karl-Fischer et division de la quantité d'humidité ainsi obtenue par la teneur du dioxyde de titane fluoré en surface (g).
  10. Composition de résine thermoplastique selon la revendication 9, où la composition contient 20 à 80 % en masse de pigment de particules de dioxyde de titane fluoré en surface.
  11. Composition de résine thermoplastique selon la revendication 9 ou 10 où le dioxyde de titane contient 0,001 à 0,2 parties en masse, pour 100 parties en masse de dioxyde de titane, d'au moins un oxyde parmi l'oxyde d'aluminium, l'oxyde de silicium et l'oxyde de zirconium et est fluoré de sorte que la teneur en fluor de la surface est 0,001 à 61 % en masse et où la composition est obtenue par malaxage du pigment particulaire avec une résine thermoplastique.
  12. Mélange maître d'une composition de résine thermoplastique contenant un pigment de particules d'oxyde de titane fluoré en surface qui est un mélange maître d'une composition de résine thermoplastique contenant une grande concentration de pigment de dioxyde de titane pour former un revêtement sur un substrat, où la composition comprend le pigment de particules d'oxyde de titane fluoré en surface qui peut être obtenu par une réaction comprenant le chauffage de particules d'oxyde de titane puis la réaction des particules d'oxyde de titane avec du gaz fluor, où le pigment de particules d'oxyde de titane fluoré en surface a une surface sensiblement fluorée et une teneur en eau de 10 à 1 400 ppm, déterminée par conditionnement à l'humidité de 3 g de la composition dans une atmosphère de 60°C et d'une humidité relative de 60 % pendant 4 heures, exposition de la composition ainsi conditionnée à un courant d'air d'humidité absolue de 0,009 kg H2O/kg d'air sec à 80°C pendant 4 heures, dégazage de la composition à 300°C pendant 30 minutes, mesure de la teneur en humidité (g) de la composition au moyen d'un dispositif de mesure d'humidité de Karl Fischer et division de la valeur obtenue par la teneur de dioxyde de titane fluoré en surface (g).
  13. Mélange maître d'une composition de résine thermoplastique selon la revendication 12 où le mélange maître contient 30 à 80 % en masse de pigment de particules d'oxyde de titane fluoré en surface.
  14. Mélange maître moulé d'une composition de résine thermoplastique contenant un pigment de particules de dioxyde de titane fluoré en surface selon la revendication 12 ou 13 où le dioxyde de titane contient 0,001 à 0,2 parties en masse, pour 100 parties en masse de dioxyde de titane, d'au moins un oxyde parmi l'oxyde d'aluminium, l'oxyde de silicium et l'oxyde de zirconium et est fluoré de sorte que la teneur en fluor de la surface est 0,001 à 61 % en masse et où le mélange maître moulé est obtenu par malaxage du pigment particulaire avec une résine thermoplastique et extrusion de la composition résultante en même temps qu'un substrat.
  15. Papier revêtu de résine photographique comprenant la composition de résine thermoplastique selon l'une quelconque des revendications 9 à 11, le mélange maître selon la revendication 12 ou 13 ou le mélange maître moulé selon la revendication 14.
  16. Composition de résine thermoplastique comprenant une résine thermoplastique et une particule d'oxyde de titane ou d'oxyde d'étain fluoré en surface, où la particule d'oxyde métallique est produite par une réaction comprenant le chauffage de particules d'oxyde de titane ou d'oxyde d'étain puis la réaction de chacune avec du gaz fluor.
  17. Procédé pour réduire l'activité de catalyseur photochimique du dioxyde de titane comprenant une réaction comprenant le chauffage de particules de dioxyde de titane puis la réaction des particules de dioxyde de titane avec du gaz fluor.
EP97122415A 1996-12-19 1997-12-18 Particules d'oxyde de métal fluorées en surface, procédé pour les préparer et leur utilisation Expired - Lifetime EP0849337B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP339806/96 1996-12-19
JP33980696 1996-12-19
JP33980696 1996-12-19
JP7389997 1997-03-26
JP7389997 1997-03-26
JP73899/97 1997-03-26

Publications (3)

Publication Number Publication Date
EP0849337A2 EP0849337A2 (fr) 1998-06-24
EP0849337A3 EP0849337A3 (fr) 1999-04-21
EP0849337B1 true EP0849337B1 (fr) 2004-03-31

Family

ID=26415042

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97122415A Expired - Lifetime EP0849337B1 (fr) 1996-12-19 1997-12-18 Particules d'oxyde de métal fluorées en surface, procédé pour les préparer et leur utilisation

Country Status (3)

Country Link
EP (1) EP0849337B1 (fr)
AT (1) ATE263215T1 (fr)
DE (1) DE69728363T2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1298430A (zh) * 1998-04-22 2001-06-06 昭和电工株式会社 表面被均匀氟化的粒状金属氧化物及其制造方法和用途
US8536083B2 (en) 2004-09-01 2013-09-17 Shell Oil Company Olefin epoxidation process, a catalyst for use in the process, a carrier for use in preparing the catalyst, and a process for preparing the carrier
JP2014070091A (ja) * 2012-09-27 2014-04-21 Nippon Shokubai Co Ltd 基材粒子表面にフッ素を含む無機顔料粒子
CN115403431B (zh) * 2022-08-25 2023-12-22 四川大学 一种气相氟化改性铝粉及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2605855B2 (ja) * 1989-01-26 1997-04-30 三菱マテリアル株式会社 導電性酸化スズ粉末の製造法
JPH0340919A (ja) * 1989-07-06 1991-02-21 Idemitsu Kosan Co Ltd 表面フッ素化超微粒子状酸化チタンおよびその製造法
JPH0680901A (ja) * 1992-08-31 1994-03-22 Mitsubishi Pencil Co Ltd 分散性改質顔料

Also Published As

Publication number Publication date
DE69728363D1 (de) 2004-05-06
ATE263215T1 (de) 2004-04-15
EP0849337A2 (fr) 1998-06-24
DE69728363T2 (de) 2005-03-10
EP0849337A3 (fr) 1999-04-21

Similar Documents

Publication Publication Date Title
US6281277B1 (en) Homogeneously surface-fluorinated metal oxide particulates, process for manufacturing the same, and use of the same
US6245140B1 (en) Surface-fluorinated metal oxide particulates, process for manufacturing the same, and use of the same
JP4278173B2 (ja) フルオロポリマー組成物のレーザーマーキング
EP0748361B1 (fr) Resistance des polymeres a la decoloration grace a l'incorporation de pigments de blanc de titane traites au silane
US6126915A (en) Titanium dioxide reduced in volatile water content, process for producing the same, and masterbatch containing the same
JP2000007941A (ja) 表面が均一にフッ素化された粒子状酸化金属、その製造方法及び用途
US20060264552A1 (en) Lower-energy process for preparing passivated inorganic nanoparticles
EP0791036B1 (fr) Pigment de dioxyde de titane ameliore revetu de dioxyde de silicium et d'oxyde d'aluminium modifies par anhydride borique
EP0707051A1 (fr) Particules inorganiques revêtues d'un acide alkylphosphonique ou d'un ester de celui-ci, leur préparation et leur utilisation
JPH1060157A (ja) 二酸化チタン顔料含有熱可塑性樹脂組成物およびマスターバッチ並びにそれらの製造方法
JPH10324505A (ja) 表面フッ素化粒子状酸化金属、その製造方法及び用途
WO2001032787A1 (fr) Traitement de carbonates metalliques alcalino-terreux particulaires
CA2390657C (fr) Procedes de preparation de pigments d'oxyde hydrophobe inorganique
EP0849337B1 (fr) Particules d'oxyde de métal fluorées en surface, procédé pour les préparer et leur utilisation
EP1484364B1 (fr) Procede de production de pigment de dioxyde de titane et compositions de resine contenant ce pigment
EP1256550B1 (fr) Procede de preparation de particules d'oxyde ultrafines a cristal mixte
EP1068031A1 (fr) Traitement des particules des carbonates de metaux alcalino-terreux
JP2000143984A (ja) フッ素化ポリイミド樹脂組成物及びその製造方法
JP2003335979A (ja) 二酸化チタン顔料の製造方法及び該二酸化チタン顔料を配合した樹脂組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 19991020

AKX Designation fees paid

Free format text: AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20010328

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040331

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69728363

Country of ref document: DE

Date of ref document: 20040506

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040630

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040630

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040712

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20041014

Year of fee payment: 8

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20041215

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050221

Year of fee payment: 8

26N No opposition filed

Effective date: 20050104

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20051218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040831